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Type: Artigo de periódico
Title: Reaction of bis(2,4-dinitrophenyl) phosphate with hydrazine and hydrogen peroxide. Comparison of O- and N-phosphorylation
Author: Domingos, JB
Longhinotti, E
Brandao, TAS
Santos, LS
Eberlin, MN
Bunton, CA
Nome, F
Abstract: Nonionic hydrazine reacts with anionic bis(2,4-dinitrophenyl) phosphate (BDNPP), giving 2,4dinitrophenyl hydrazine and dianionic 2,4-dinitrophenyl phosphate by an S(N)2(Ar) reaction, and at the phosphoryl center, giving 2,4-dinitrophenoxide ion and a transient phosphorylated hydrazine that rearranges intramolecularly to N-(2,4-dinitrophenyl)-N-phosphonohydrazine. Approximately 58% of the reaction at pD = 10 occurs by N-phosphorylation, as shown by P-31 NMR spectroscopy. Reaction of HO2- is wholly at phosphorus, and the intermediate peroxophosphate reacts intramolecularly, displacing a second 2,4-dinitrophenoxide ion, or with H2O2, giving 2,4-dinitrophenyl phosphate and O-2. Rate constants of O- and N-phosphorylation in reactions at phosphorus of NH2NH2, HO2-, and NH2OH and its methyl derivatives follow Bronsted relationships with similar slopes, but plots differ for oxygen and nitrogen nucleophiles. The reaction with NH2NH2 has been probed by using both NMR spectroscopy and electrospray ionization mass and tandem mass spectrometry, with the novel interception of key reaction intermediates in the course of reaction.
Country: EUA
Editor: Amer Chemical Soc
Citation: Journal Of Organic Chemistry. Amer Chemical Soc, v. 69, n. 23, n. 7898, n. 7905, 2004.
Rights: fechado
Identifier DOI: 10.1021/jo048737k
Date Issue: 2004
Appears in Collections:Unicamp - Artigos e Outros Documentos

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